Activated protective carbon



Patented June 13, 1950 ACTIVATED rnorso'rrvn CARBON J'acoue C. Morrell and George T. Tohiasson. Chica e. Ill, assi nors. by mesne assignments. to the Un ted States of America as represented by the Secretary of War No Drawin A lication May 1, 1942, Serial No. 441,272

2 Claims.

The invention described herein may be manufactured and used by or for the Government for governmental purposes, without the payment to us of any royalty thereon.

This invention relates to the improvement of adsorbent materials for use as gas absorbents in gas masks and shelters. It relates more particularly to a process for depositing active catalysts upon adsorbent surfaces such as those of activated carbons to improve by chemical and catalytic, as well as by adsorptive means, the ability of the surfaces to remove poisonous gases from gaseous mixtures.

Activated carbons which may be treated to improve their activity for removing poisonous gases and vapors from air are obtainable from several sources. Coconut charcoal is produced from coconut shells which are dried, then carbonized and activated at a temperature of from about 1600 to about 1700 F. in the presence of steam or of a mixture of steam and flue gas which may contain small amounts of air, and in some activation treatments, air is used as such. Fruit pits are also convertible into activated chars by using similar methods. Other activated carbons, generally referred to as domestic or synthetic chars, may be manufactured from coal, coke, wood, or wood charcoal or various mixtures of the same, employing in some cases specific types of coal with or without the addition of wood char. Such carbonaceous material is generally dried, ground to a fine powder, mixed with a binder as pitch, and briquetted; after which the briquettes are crushed to give granular material of about 6 to 20 mesh particle size. The components may also be treated with various chemical reagents before mixing. Similarly wood may be treated with reagents such as zinc chloride and subsequently carbonized and activated. This granular material is then carbonized and activated following the general procedure mentioned for producing coconut char.

Broadly, an activated carbon or other material is said to absorb a poisonous gas or vapor from air or other gas mixture when it substantially removes said gas or vapor by any means. which may include adsorption, oxidation, etc. Heretofore a number of metal compounds have been deposited on activated carbons to increase their abilities to absorb poisonous gases and vapors from air containing them. If these metal compounds, copper oxide is a particularly important example. One method previously used for depositing active copper oxide on an adsorbent to produce an absorptive material comprises preparing a solution of a copper ammonium carbonate complex, impregnating the adsorbent with the solution and subsequently heating to dry the impregnated material and to convert deposited salts into an active copper oxide, especially to cupric oxide. Thus in an established practice, ammonia, carbon dioxide, and air are bubbled through a reactor column containing water and scrap copper for a more or less prolonged period of time until a solution is formed which contains approximately 7 to 9 per cent by weight of copper, 10 to 12 per cent of ammonia, and 5 to 6 per cent of carbon dioxide by analysis. The adsorbent or char is impregnated with this solution by wetting or soaking, and is subsequently drained to remove the excess solution. The impregnated material is then heated to dry it and to decompose the deposited copper ammonium carbonate complex and to drive off carbon dioxide and ammonia. Recently it has been found that the absorptive properties of absorbents may be improved by increasing the ammonia and carbon dioxide content of the impregnating solution, either by fortiiying this solution by further addition of ammonia and carbon dioxide, or by the addition to the solution of ammonia and salts such as basic copper carbonate and ammonium carbonate. The solution may also be prepared entirely from these compounds. v

Heretofore the absorptive capacity of impregnated chars prepared as above indicated has been further improved by secondary impregnation. Thus a dried activated carbon impregnated with copper ammonium carbonate complex has been further impregnated using a solu-' tion containing approximately 5.0 per cent by weight of sodium hydroxide and about 0.5 per cent of sodium thoiocyanate, and has then been dried carefully to obtain a carbon having increased absorptiveness for gases such as cyanogen chloride. It has also been found that as a result of this secondary impregnation the absorbent may deteriorate in storage or take on moisture much more readily.

Because of this deterioration or humidification, the absorptive capacity of the absorbent for arsine is greatly reduced and under some conditions that are encountered, such as tropical conditions, the amount of moisture taken up is so large that the absorption is practically nil. The effect of this deterioration has been noted to a varying degree in the decrease in absorption of other poisonous gases.

Previously the absorptive capacities of activated carbons have also been improved by other secondary treatments. Thus activated carbon as such or after impregnation with copper oxide has been sprayed with a solution of silver nitrate to obtain absorbents .having 1. increased absorptivenessparticularly to. arsine when the. absorbents are used under humid conditions. Although the absorptive capacity has been improved by the secondar treatment, this form of treatment has the disadvantage'that the silver is rather poorly distributed:onthe-absorbent and also this spraying treatmentmay result in a lowered capacity of the absorbent for the absorption of acid gases such as hydrocyanic acid.

It is among the objects of .the present in vention to gain advantages resulting from-the separate treatments above described, but to avoid the secondary treating methods=previous ly employed and thereby to minimize or substantially .-elimina'te deleterious efiects arising from their use. Awfurtherrimportantpbiect'is'to simplify the impregnating-pr:treating" procedure .by. reducing the number of operations'necessary ,to produce-char :with-high'absorptive properties. Of .great importance is the iact that'the impreg .nating ina=single stage onstep;produoesjnsoluble cyanate givesaproduct from whichsodi..v hiocyanateis: readily removednby-awater. Other objects of the: invention will be apparentdrom the followingdescription.

In -,one specific -;embodiment the present invention comprises -a process :for :preparing ab sorbentscflhigh-activityfor removing poisonous fluids from gas mixtures, :andparticularly from air contaminated thereby, which comprises preparinga solution of'copper: ammonium carbonate complex, adding-to said; solution 'a soluble silver compound =and.asoluble th-iocyanate, forming a composite or integrated --solution, impregnating an: activated carbon with said composite solution, and heating the impregnatedmaterial to-:remove water-end-volatile products to form an impregnated carbonof :highly improved absorptive *capacity, for poisonous fluids and particularly gases and vapors.

-. Inca vfurtherembodiment, an alkaline material is also added to the composite solution employed for impregnating the .char.

.According -to the simplified process -of :the present invention, which we herein refer" to 1 as an integrated process, improved gas-.-absorbents are produced by means ofa single impregnating step anda heating operation. Theimpregnated absorbents produced have --a-lso been --shown to have difi'erent chemical -.structure from absorbents of the prior art -when subjected to chemical analysis.

In carrying out the process of the invention, a solution of copper ammoniumcarbonate complex, preferably with-a relatively high ammonia content is prepared and a soluble thiocya-nate and a soluble silver compound.are incorporated therein. Thus silver nitrate for example, is "dissolved in water to -form .a rather concentrated solution-such-asone containing to 50 per cent, moreor less,=ofrsilvernitrate, and this-solution is addedgraduallyavith'stirringto the copper-ammonium carbonate solution. The concentration of the added-silversolutionds not-criticaL'as the main consideration is that-of-keeping-ata'minimum the dilution --of "the copper impregnating solution, although in some cases the concentration must be controlled and it is especially desirable to maintain an excess of water soluble silver compound over that which reacts with the thiocyanate. The greater the dilution of the silver .nitrate solution, the greater will be the diluting effect upon the .copper ammonium carbonate impregnating solution. Any precipitation effects obtained when adding the silver compound are of a temporary nature since we have found that any'precipitate formed is readily re- .dissolved while theagitation or stirring is continued. The amount of silver added to the copper "solution may-varygenerally upwards to 0.1 per -cent by weight -or more, but preferably the amount of soluble silver salt added to the solution is such as to deposit on the absorbent approximately 0.02' to about 0.05 per cent of silver. Whenan amount of silver nitrate corresponding to this amount of silver is used, there is little or no evidence of -a :segregation of vsediment on standing after adding the .thiocyanate 'in'the 'amountof emgsflfiper cent, 18.5 Willbe subsequently described. Inmostrcases however it-is "desirable to increase thesilver concentrationand reduce the thiocyanateconcentration down to say 0.25 percent.

In the-case of domestic char-where activating agencies such as zinc chloride are used, anions suches. chlorine shouldbe practically completely removed fromthe adsorbentsurfaees prior "to impregnating treatment.

Similarly, a soluble thiocyanate such-as sodium'sthiocyanate may-be dissolved in water to form aTrather concentrated 'sol-utionsuch 'as a .10 to -50-percent-solution,-and theth-iocyanate solution may be gradually added to the copper solution-whilestirring. We have found thatany precipitation effects which may occur at this point are of a temporary nature since' the precipitate is readily redissolved while continuing the agitatingor stir-ring. The amount' of-th-iocyanate to be :added to the copper-'solutionmay vary upwards to.2.-0-per -.cent-or more, depending upon-costs, the type-"ofabsorbent base,-and;.the product desired. In'many preparationswe have found thatapprox-imately 0:5 per centof'sodium th-iocyanate gives good results, but when the amount of silver-corresponding to this concentration causes precipitation when added it is preferable to reduce the thiocyanate concentration and increasethesilverto have an excessof thelatter.

Further, a small amount of alkalimay also be addedto-thecopper impregnating solution in addition to .the thiocyanate. After addition of too large an amount of alkali, undesirable effects havebeen observedin the hydrationcharacteristics ofuthe resultant-absorbent. Thus, we have observedfor example, thatforsome chars the addition-of- 5.0 per-centby weight ofsodium hydroxide is undesirable whereastheadditionof approximately 1.0 per cent ofsodiumhydroxidehas desirable efiects in increasing the absorption-or removalof.somepoisonous gases.

.In the addition of soluble thiocyanates .and silvercompounds .to-the copper-ammonium carbonate solution, there is-no limitation as to the manner ororder in which these areadded since theymay, for example, be included with the copper solution during .its rpreparation with .good results. In aless preferred embodiment of the invention, the thiocyan-ate .may 'be incorporated in'the copper-containing solution, the char may be impregnatedthereby, and after draining from excess solution, drying and calcining, the impregnated char may then be sprayed with a solution containing the silver compound.

According to the process of the present invention the adsorbent or charcoal to be impregnated is Wetted by the impregnating solution in any desirable manner. Thus, for example, a char is soaked in the solution and the excess solution is drained from the impregnated material. The wetted char is then directed to drying and conversion or calcining treatment to remove moisture and to decompose the copper ammonium carbonate complex and some of the other impregnated compounds, and to remove gaseous de composition products which are largely ammonia and carbon dioxide. Thus, the wet impregnated char may be directed to a rotary dryer and raised to a temperature of about 300 F. so as to efiect the desired drying and conversion treatment. The maximum temperature used during drying and calcining varies somewhat with the type of char employed and the nature of the impregnating solution So that in some instances, temperatures as high as 400 to 500 F. may be used for a short period of time without substantial detrimental effects to the impregnated char. More frequently, however, the temperature employed may be from about 275 to about 356 F. and care should be observed so that the char does not ignite at high temperatures in the presence of air as a result of the metal oxide catalysts deposited thereon. After cooling, the chars are packed in air-tight containers to exclude moisture and other readily absorbed materials. The characteristics of several impregnated chars will be illustrated in the specific examples hereinafter set forth.

It is apparent from the above description of the process that considerable savings in equipment and labor costs are thus effected since only a single impregnation and a drying treatment are employed instead of a series of impregnations and drying and calcining steps or other prelimlnary or secondary treatments heretofore employed. Besides the above indicated advantages of the process the impregnated and calcined charcoal is much more absorptive for poisonous. gases, liquids, and vapors than the product obtained by the methods of the prior art. Thus for example, it has been found previously that when sodium thiocyanate is employed in the impregnation, the sodium thiocyanate may be substantially extracted with water from the impregnated char produced by the twostage impregnation of the prior art, whereas the char product of our one-stage or integrated impregnation gives up very little sodium thiocyanate when extracted with water. It is not known exactly why the char impregnated by the present process is superior to that of the prior art but it may be due in part to factors such as the presence of copper thiocyanate, the presence of less undecomposed copper carbonate salts, and better distribution of silver on the absorbent surfaces.

The following examples are given to illustrate the integrated process of impregnating activated carbon and some of the results obtained in employing these materials for removing poisonous gases from air, although the data given are not intended to limit the broad scope of the invention.

An impregnating solution was prepared by bubbling ammonia, carbon dioxide, and air through a reactor containing copper wire and water to form an intermediate solution of copper ammonium carbonate complex found by analysis to'contain 7.7 per cent by weight of copper, 8.0 per cent of ammonia, and 4.6 per cent of carbon dioxide. This intermediate solution was then fortified with aqueous ammonia, hydrated copper carbonate, and ammonium carbonate to form a solution which upon analysis was found to contain approximately 10 per cent by weight of copper, 16 per cent of ammonia, and 11 per cent of carbon dioxide. Silver nitrate in the form of a 50 per cent aqueous solution was gradually stirred into the copper impregnating solution in an amount so as to deposit approximately 0.023 per cent by weight of silver on the charcoal to be impregnated. Subsequently approximately 0.5 per cent by weight of sodium thiocyanate as a 50 per cent aqueous solution was added gradually with stirring to the composite or integrated solution containing the copper and silver compounds.

A 6 to 20 mesh coconut charcoal suitable for use in gas masks was impregnated with this solution at room temperature and the excess solution was drained oif. The impregnated char was then dried for several hours and gradually raised to a temperature of approximately 300 F. Another char was similarly prepared employing the same procedure as above with the exception that twice as much silver nitrate was added to the copper impregnating solution. It was observed in connection with the above impregnating solutions that while no separation or sedimentation of insoluble matter such as silver thiocyanate was apparent when using the lower concentration of added silver, there was a slight formation and segregation of insoluble matter when employing the higher silver concentration. These chars were tested according to the oflicial C. W. S. tube test procedures against air mixtures containing hydrocyanic acid, arsine, and cyanogen chloride, respectively. A char prepared in a similar manner but impregnated with only the ammonium copper carbonate solution was also tested. Results of these comparative tests were as follows:

Gas Lives in Minutes When Tested on Char Impregnated With HON Arsi'ne CNCl Copper Solution Only 135 57 Copper Solution with Low Silver Concentration 147 122 75 Copper Solution with Higher Silver Concentration 153 99 71 Of much greater significance, however, are the following life test results which were obtained for these chars on arsine and cyanogen absorptiveness under conditions simulating the conditions of the tropics using highly humidified chars.

It is apparent from the above data that chars after treatment according to the process of the present invention had higher gas absorptiveness for all of the typical poisonous test gases than did the char impregnated by the methods of the prior art. The chars impregnated by the present process have this high absorptiveness not only when amines employed underctemperate:conditions butxsneci- .ally when :employed under tropical :conditions with high relative humidity.

The character of .the invention. and the type of results obtained by its usezare evident -from-the preceding specification and examples, although :they are not to be construed as-zto impose undue limitations upon the generally broad :scope-of :the invention.

We claim as our invention:

1. A:catalytie producthaving high activity for removing poisonous gases-from air contaminated dzhereby, said product consisting predominantly :of activated :carbon impregnated with minor proportions of ;metal compounds which impart 8 -2. fllhe producto! ;c1aim;1 in which theactlvatedrcairbonis impregnated with an aqueous ammonium:solutionfconsistingby weight of approximately 10 :percent .of copper, 15 percent ammonia. 1'1i1;'percentcarbon dioxide, .05 percent "thiocyanateand slightly more than a trace of :silver nitrate.

JAQQUE C. MORRELL. 'rGEORGE T. TOBIASSON.

QREFERENCES CITED The followingyreferences are of recordin the file of this :patent:

UNITED STATES PATENTS "Number Name Date 1,519,470 .wilsdn Dec. 16,1924 1,540,447 Wilson June 2, 1925 1,995,274 ,Eversole. ,Mar. 19,1935

, 2,212,593 ,Dittrich. Aug. 27. 1940 

1. A CATALYTIC PRODUCT HAVING HIGH ACTIVITY FOR REMOVING POISONOUS GASES FROM AIR CONTAMINATED THEREBY, SAID PRODUCT CONSISTING PREDOMINANTLY OF ACTIVATED CARBON IMPREGNATED WITH MINOR PROPORTIONS OF METAL COMPOUNDS WHICH IMPART TO THE ACTIVATED CARBON A LONG ARSINE LIFE, SAID COMPOUNDS BEING SUBSTANTIALLY DRY COPPER OXIDE, COPPER THIOCYANATE, SILVER THIOCYANATE AND A WATER SOLUBLE SODIUM COMPOUND, SAID SILVER THIOCYANATE CONSTITUTING BETWEEN 0.01 AND 0.05 PERCENT OF SAID PRODUCT AND EACH OF THE OTHER OF SAID COMPOUNDS CONSTITUTING BETWEEN 0.03 PERCENT AND 5.0 PERCENT OF THE PRODUCT. 